EP3027631B1 - Prozess zur herstellung von verbrückten metallocenkomplexen geeignet für die olefinpolymerisierung - Google Patents
Prozess zur herstellung von verbrückten metallocenkomplexen geeignet für die olefinpolymerisierung Download PDFInfo
- Publication number
- EP3027631B1 EP3027631B1 EP14747576.8A EP14747576A EP3027631B1 EP 3027631 B1 EP3027631 B1 EP 3027631B1 EP 14747576 A EP14747576 A EP 14747576A EP 3027631 B1 EP3027631 B1 EP 3027631B1
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- EP
- European Patent Office
- Prior art keywords
- group
- formula
- carbon atoms
- chosen
- butyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000001336 alkenes Chemical class 0.000 title description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 16
- 238000006116 polymerization reaction Methods 0.000 title description 13
- -1 N-substituted 2-bromoaniline Chemical class 0.000 claims description 62
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 239000003446 ligand Substances 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- PLVCYMZAEQRYHJ-UHFFFAOYSA-N (2-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Br PLVCYMZAEQRYHJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 3
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052735 hafnium Inorganic materials 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 3
- VBMIZCKXRRAXBK-UHFFFAOYSA-N 1h-inden-2-ylboronic acid Chemical compound C1=CC=C2CC(B(O)O)=CC2=C1 VBMIZCKXRRAXBK-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VCXLJLNFTUCEER-UHFFFAOYSA-N OB(O)c1ccccc1C1=Cc2ccccc2C1 Chemical compound OB(O)c1ccccc1C1=Cc2ccccc2C1 VCXLJLNFTUCEER-UHFFFAOYSA-N 0.000 description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004653 anthracenylene group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 2
- 125000004976 cyclobutylene group Chemical group 0.000 description 2
- 125000005725 cyclohexenylene group Chemical group 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 125000004979 cyclopentylene group Chemical group 0.000 description 2
- 125000004980 cyclopropylene group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012968 metallocene catalyst Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005548 pyrenylene group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000005628 tolylene group Chemical group 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical group OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 description 1
- CCUYEVNCRQDQRF-UHFFFAOYSA-N 2-bromo-1h-indene Chemical compound C1=CC=C2CC(Br)=CC2=C1 CCUYEVNCRQDQRF-UHFFFAOYSA-N 0.000 description 1
- MJDIPICYXPOZEM-UHFFFAOYSA-N 2-bromo-n-tert-butylaniline Chemical compound CC(C)(C)NC1=CC=CC=C1Br MJDIPICYXPOZEM-UHFFFAOYSA-N 0.000 description 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 1
- STNDIHAVRCIBCC-MDZDMXLPSA-N 3-[(e)-2-phenylethenyl]aniline Chemical class NC1=CC=CC(\C=C\C=2C=CC=CC=2)=C1 STNDIHAVRCIBCC-MDZDMXLPSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- CDHICTNQMQYRSM-UHFFFAOYSA-N di(propan-2-yl)alumane Chemical compound CC(C)[AlH]C(C)C CDHICTNQMQYRSM-UHFFFAOYSA-N 0.000 description 1
- KVSQODQSFPXWBD-UHFFFAOYSA-N dibutyl(ethoxy)alumane Chemical compound CCCC[Al](OCC)CCCC KVSQODQSFPXWBD-UHFFFAOYSA-N 0.000 description 1
- KBLZFQBDODEHJH-UHFFFAOYSA-N dibutylalumane Chemical compound C(CCC)[AlH]CCCC KBLZFQBDODEHJH-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- IAAKXIPQVRCQAY-UHFFFAOYSA-N difluoro-(2,3,4,5,6-pentafluorophenyl)borane Chemical compound FB(F)C1=C(F)C(F)=C(F)C(F)=C1F IAAKXIPQVRCQAY-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- MNFTYNIMQNJVJI-UHFFFAOYSA-N ethoxy(dipropyl)alumane Chemical compound CC[O-].CCC[Al+]CCC MNFTYNIMQNJVJI-UHFFFAOYSA-N 0.000 description 1
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 description 1
- UYONORMOFAZUJY-UHFFFAOYSA-N ethoxy-di(propan-2-yl)alumane Chemical compound CC[O-].CC(C)[Al+]C(C)C UYONORMOFAZUJY-UHFFFAOYSA-N 0.000 description 1
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- DBTNVRCCIDISMV-UHFFFAOYSA-L lithium;magnesium;propane;dichloride Chemical compound [Li+].[Mg+2].[Cl-].[Cl-].C[CH-]C DBTNVRCCIDISMV-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- YNLPNVNWHDKDMN-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CC[CH-]C YNLPNVNWHDKDMN-UHFFFAOYSA-M 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229920006302 stretch film Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CQXDYHPBXDZWBA-UHFFFAOYSA-N tert-butyl 2,2,2-trichloroethanimidate Chemical compound CC(C)(C)OC(=N)C(Cl)(Cl)Cl CQXDYHPBXDZWBA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/48—N-alkylated amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
-
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
Definitions
- the invention relates to a process to prepare a metallocene complex.
- metallocene complexes are not well established due to difficulties faced in metallocene synthesis and polyolefin production process.
- metallocene complexes for the synthesis of polyolefins, preferably polyethylenes in the industry.
- Bridged metallocene complexes are known in the state of the art and are for instance described in WO94/11406A1 and in US6342622 .
- metallocene complexes are described comprising two cyclopentadienyl or indenyl ligands that are bridged with a bridging group comprising sp3 or sp2 hybridized carbon atoms.
- a different class of metallocene complexes comprising one cyclopentadienyl ligand connected via a bridge with a heteroatom, chosen from oxygen, sulfur, nitrogen or phosphorus. This heteroatom is also bonded to the metal in the metallocene complex.
- the bridging group can comprise carbon atoms, silicon atoms, germanium atoms and boron atoms.
- WO2008/084931 discloses transition metal complexes comprising a bidentate ligand having a monocyclopentadienyl group coupled to an amido group.
- monocyclopentadienyl groups are cyclopentadienyl, 1-indenyl and fluorenyl groups.
- Wu et al. (DOI: 10.1021/om800317v) report on CO 2 -mediated ortho-lithiation of n-alkylanilines and their use in the construction of polymerisation catalysts.
- KR2010113336A reports on catalyst compositions for polyolefins with good heat resistance and narrow polydispersity.
- Lee et al. (DOI:10.1016/j/jorganchem.2007.11.021) report on o-phenylene bridged Cp/amido titanium and zirconium complexes and their polymerisation reactivity.
- WO2007078134A1 reports on half-sandwiched constraint-geometry transition metal phenylene-bridged pendant phosphido and amido complexes as alkene polymerisation and copolymerisation catalysts.
- WO2007078133A1 reports on a catalyst composition comprising group 4 transition metal complexes.
- Cho et al. (DOI: 10.1021/OM0601854) report on o-phenylene-bridged Cp/amido titanium complexes for ethylene/1-hexene copolymerisations.
- KR2010083076A reports on a catalyst composition containing transition metal compounds for heat-resistant polyolefin polymerization.
- JP2011153201A reports on a diarylaminopyrene material, organic electroluminescent device, and ink composition thereof.
- Yang et al. (DOI: 10.1021/jp0517807) report on excited-state behavior of n-phenyl-substituted trans-3-aminostilbenes.
- JP2012028711A reports on a material comprising polycyclic aromatic compound, organic electroluminescent device, and ink composition therefor.
- Lensink et al. DOE: 10.1107/S16005368020
- Suitable metallocene complexes for the synthesis of polyolefins may for example be metallocene complexes according to formula 1 wherein
- the metallocene complex comprises a metal selected from lanthanides or transition metals from group 3, 4, 5 or 6 of the Periodic System of the Elements.
- the Periodic System of the Elements is understood to be the Periodic System of the Elements that can be found at www.chemicool.com.
- the metal M is preferably chosen from the group consisting of Ti, Zr, Hf, V and Sm, more preferably from Ti, Zr and Hf, most preferably the metal is Zr.
- Q is an anionic ligand to M.
- the Q ligands preferably are the same and are selected from the group consisting of halogen (F, CI, Br, I) and hydrocarbyl groups comprising 1 to 20 carbon atoms. More preferably the Q ligands are Cl or a methyl group.
- k is the number of Q groups and equals the valence of M minus 2; k is an integer. Preferably, k is 2.
- X is a cyclic bridging group.
- X is bridging between a carbon atom of the cyclopentadienyl ligand and nitrogen.
- X can contain both sp3 and sp2 hybridized carbon atoms.
- the cyclic bridging group X can be monocyclic or polycyclic.
- the cyclic bridging group X may comprise fused rings.
- cyclic bridging groups are phenylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclohexenylene, cyclohexadienylene, tolylene, benzylene, naphthylene, anthrylene, pyrenylene, biphenylene and binaphthylene.
- the cyclic bridging group can be substituted with alkyl groups having 1 to 10 carbon atoms, for example the substituents may be selected from the group of methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl.
- X carries less than 10 substituents, more preferably less than 5 substituents and most preferably no substituents.
- X preferably is chosen from the group consisting of a phenylene and a biphenylene group. Most preferably X is chosen from the group consisting of a 1,2 phenylene group and a 2,2'-biphenylene group.
- Z 1 and Z 4 are identical or different and can be chosen from the group of hydrogen and a hydrocarbon radical with 1-20 carbon atoms.
- Hydrocarbon radicals can be alkyl, aryl or aryl alkyl substituents.
- alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
- aryl groups are phenyl, mesityl, tolyl, and cumenyl.
- aryl alkyl substituents are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
- Adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound.
- Z 2 and Z 3 are connected to form 6 membered ring such as phenyl, substituted phenyls, hydrogenated phenyls or substituted hydrogenated phenyls, wherein preferred substitutions are alkyl groups, as part of an indenyl or tetrahydroindenyl ring system.
- Z 1 and Z 4 are hydrogen. Most preferably Z 1 and Z 4 are hydrogen and Z 2 and Z 3 are connected, such that a 2-indenyl ligand or a 2-tetrahydroindenyl ligand is formed.
- R is chosen from the group of hydrogen and a hydrocarbon radical with 1-20 carbon atoms.
- Hydrocarbon radicals can be alkyl, aryl or aryl alkyl substituents.
- alkyl groups are methyl, ethyl, propyl, butyl, hexyl and decyl.
- aryl groups are phenyl, mesityl, tolyl, and cumenyl.
- aryl alkyl substituents are benzyl, pentamethylbenzyl, xylyl, styryl and trityl.
- R is preferably an alkyl group with 1-10 carbon atoms, more preferably with 1-6 carbon atoms.
- Preferably R is a branched alkyl, more preferably R is isopropyl or t-butyl. Most preferably R is a t-butyl group.
- Suitable metallocene complexes for the synthesis of polyolefins may for example be according to formula 2 wherein M is chosen from the group of Ti, Zr and Hf, and wherein Z 1 and Z 4 are identical or different and can be chosen from the group consisting of hydrogen or a hydrocarbon radical with 1-20 carbon atoms;adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound and R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group ; Q is Cl or a methyl group; and k is the number of Q groups and equals the valence of M minus 2; k is an integer.
- Suitable metallocene complexes may also for example be according to formula 3 wherein M is chosen from the group of Ti, Zr and Hf, and wherein Z 1 and Z 4 are identical or different and can be chosen from the group consisting of hydrogen or a hydrocarbon radical with 1-20 carbon atoms;adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound and R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group ; Q is Cl or a methyl group; and k is the number of Q groups and equals the valence of M minus 2; k is an integer.
- a suitable metallocene complex may for example contain a 2-indenyl group and is represented by the formula 4 wherein M is chosen from the group of Ti, Zr and Hf, and wherein X is a cyclic bridging group, R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms ; Q is Cl or a methyl group; and k is the number of Q groups and equals the valence of M minus 2; k is an integer.
- M is Zr
- R is t-butyl
- Q is Cl or methyl
- k 2
- X is chosen from the group consisting of phenylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclohexenylene, cyclohexadienylene, tolylene, benzylene, naphthylene, anthrylene, pyrenylene, biphenylene and binaphthylene, most preferably X is chosen from the group of 1,2-phenylene and 2,2'-biphenylene.
- Another suitable metallocene complex may for example be according to formula 6 wherein M is chosen from the group of Ti, Zr and Hf, and wherein R is chosen from the group of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group ; Q is Cl or a methyl group; and k is the number of Q groups and equals the valence of M minus 2; k is an integer.
- M is Zr
- R is t-butyl
- Q is Cl or methyl
- k 2.
- the metallocene complex can be supported on a support.
- the support is preferably an inert support, more preferably a porous inert support.
- porous inert supports materials are talc and inorganic oxides.
- the support material is in a finely divided form.
- Suitable inorganic oxide materials include group 2A, 3A, 4A and 4B metal oxides such as silica, alumina and mixtures thereof.
- Other inorganic oxides that may be employed either alone or in combination with the silica or alumina are magnesia, titania, zirconia and the like.
- Other support materials can be employed, for example finely divided functionalized polyolefins such as finely divided polyethylene.
- the support is a silica having a surface area between 200 and 900 m 2 /g and a pore volume between 0.5 and 4 ml/g.
- the ligands can be prepared in a multiple step process.
- First an intermediate 1 (Formula 7) is prepared by reacting compounds in a solvent at a pH above 7 according to the following scheme:
- LG is a leaving group.
- Examples of LG are halides, like for example Cl or Br, or 2,2,2-trichloroacetimidate group.
- R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group.
- This intermediate 1 can react with a compound LF-B(OH) 2 , in the presence of a Pd catalyst and a Lewis base (according to a Suzuki reaction), to arrive at a ligand precursor according to the following scheme:
- LF is a ligand fragment, which is chosen from the group consisting of wherein Z 1 and Z 4 are identical or different and can be chosen from the group consisting of hydrogen or a hydrocarbon radical with 1-20 carbon atoms;adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound and R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group.
- a suitable ligand precursor may have a structure according to formula 8 wherein X is a cyclic bridging group; Z 1 and Z 4 are identical or different and can be chosen from the group consisting of hydrogen or a hydrocarbon radical with 1-20 carbon atoms;adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound; and R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably R is a t-butyl group.
- preferred further suitable ligand precursor may have a structure according to formula 9: , wherein LF is a ligand fragment, which is chosen from the group consisting of wherein Z 1 and Z 4 are identical or different and can be chosen from the group consisting of hydrogen or a hydrocarbon radical with 1-20 carbon atoms;adjacent substituents Z 2 and Z 3 are connected to form an indenyl or tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound and R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms.
- a further suitable ligand precursor may have a structure according to formula 10 or 11
- R is chosen from the group consisting of hydrogen and a hydrocarbon radical with 1-20 carbon atoms, preferably a t-butyl group.
- Metallocene complexes according to formula 1 may for example be prepared by
- organic and inorganic bases that can be used for creating anions of the ligand precursors are methyllithium, butyllithium, sec-butyllithium, t-butyllithium, lithiumdiisopropylamide (LDA), sodiumhydride, isopropylmagnesiumchloride-lithiumchloride, s-butylmagnesiumchloride, sodiumhexamethyldisilazide, potassiumhexamethyldisilazide and combinations thereof.
- LDA lithiumdiisopropylamide
- Metallocene complexes according to formula 12 can be obtained when the following preferred process for the preparation is used.
- n-BuLi was added to a cooled solution of the ligand precursor (formula 10 or 11) in freshly dried diethyl ether under N2 atmosphere at -78°C.
- the cold bath was removed after ⁇ 30min and solution was stirred at room temperature for 4hrs.
- the solution was now again cooled to -78°C and solid ZrCl 4 was added.
- the solution was slowly brought to room temperature and further stirred for 2h.
- the solvent was then removed by filtration and the residue was washed with ether.
- the invention relates to the preparation of the metallocene complexes according to formula 5 comprising the steps of:
- Olefin polymers may be prepared by polymerizing one or more olefins in the presence of the described metallocene complex or in the presence of the described composition, wherein the metallocene complex is present on a support and a cocatalyst
- the cocatalyst employed include aluminium- or boron-containing cocatalysts.
- Suitable aluminium-containing cocatalysts comprise aluminoxanes and alkyl aluminium.
- the aluminoxanes usable are well known and preferably comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by the formula: R 3 - (AlR 3 -O) n - AlR 3 2 for oligomeric, linear aluminoxanes and (- AlR 3 - O -) m for oligomeric, cyclic aluminoxanes; wherein n is 1-40, preferably n is 10-20; m is 3-40, preferably m is 3-20 and R 3 is a C 1 to C 8 alkyl group and preferably a methyl group.
- organoaluminum compounds can be used such as trimethylaluminum, triethylaluminium, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triamylaluminium; dimethylaluminium ethoxide, diethylaluminium ethoxide, diisopropylaluminium ethoxide, di-n-propylaluminium ethoxide, diisobutylaluminium ethoxide and di-n-butylaluminium ethoxide; dimethylaluminium hydride, diethylaluminium hydride, diisopropylaluminium hydride, di-n-propylaluminium hydride, diisobutylaluminium hydride and di-n-butylaluminium hydride.
- Suitable boron-containing cocatalysts include trialkylboranes, for example trimethylborane or triethylborane and/or perfluorophenylborane and/or a perfluorophenylborate.
- an organoaluminum cocatalyst is present. More preferably, methylaluminoxane is used as the cocatalyst.
- the process to produce the olefin polymers may start with the reaction of the metallocene complex with the cocatalyst. This reaction can be performed in the same vessel as the reaction vessel wherein the olefin polymers are produced or in a separate vessel, whereafter the mixture of the metallocene complex and the cocatalyst is fed to the reaction vessel. During the reaction described above an inert solvent can be used.
- the cocatalyst is used in an amount of 10 to 100,000 mol, preferably from 10 to 10,000 mol per mol of the transition metal compound.
- the solvent used in the process to produce olefin polymers may be any organic solvent usually used for the polymerization.
- solvents are benzene, toluene, xylene, butane, pentane, hexane, heptane, cyclohexane and methylene chloride.
- the olefin to be polymerized can be used as the solvent.
- the polymerization conditions like for example temperature, time, pressure, monomer concentration can be chosen within wide limits.
- the polymerization temperature is in the range from -100 to 300 °C, preferably 0 to 200 °C, more preferably 10 to 100 °C.
- the polymerization time is in the range of from 10 seconds to 20 hours, preferably from 1 minute to 10 hours, more preferably from 5 minutes to 5 hours.
- the ethylene pressure during polymerization is in the range from 1 to 3500 bar, preferably from 1 to 2500 bar, more preferably from 1 to 1000 bar, even more preferably from 1 to 500 bar, most preferably from 1 to 100 bar.
- the molecular weight of the polymer can be controlled by use of hydrogen in the polymerization.
- the polymerization may be conducted by a batch process, a semicontinuous process or a continuous process and may also be conducted in two or more steps of different polymerization conditions.
- the polyolefin produced is separated from the polymerization solvent and dried by methods known to a person skilled in the art.
- the olefin which is polymerized can be one type of olefin or can be mixtures of different olefins.
- the polymerization thus includes homopolymerization and copolymerization.
- olefins examples include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene and styrene; conjugated and non-conjugated dienes such as butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene; and cyclic olefins such as cyclobutene, but is not limited thereto.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene and styrene
- At least one of the olefins that is polymerized is ethylene.More preferably, a mixture of ethylene and at least one other olefin of 3 or more carbon atoms is polymerized.
- a high molecular weight of the olefin polymer can be obtained.
- the other olefin of 3 or more carbon atoms is chosen from 1-butene, 1-hexene or 1-octene, more preferably the other olefin is 1-hexene.
- the olefin comonomer is present in an amount of about 5 to about 20 percent by weight of the ethylene-olefin copolymer, more preferably an amount of from about 7 to about 15 percent by weight of the ethylene-alpha olefin copolymer.
- an LLDPE having a melt mass flow rate (also known as melt flow index) as determined using ASTM D1238-10 (190°C/2.16 kg) which ranges from 1 to 125 g/10 min and a density in the range from 900 kg/m 3 to less than 940 kg/m 3 as determined using ASTM D1505-10 may be obtained.
- the density of the linear low density polyethylene ranges from about 915 kg/m 3 to less than 940 kg/m 3 , for example between 915 and 925 kg/m 3 .
- the melt flow index of the linear low density polyethylene ranges from 0.3 to 3 g/10min, for example from 0.5 to 1.5 g/10min.
- the polymerisation may be performed via a gas phase process or via a slurry process.
- the production processes of polyethylene are summarised in " Handbook of Polyethylene” by Andrew Peacock (2000; Dekker; ISBN 0824795466) at pages 43-66 .
- the catalysts can be divided in three different subclasses including Ziegler Natta catalysts, Phillips catalysts and single site catalysts.
- the latter class is a family of different classes of compounds, metallocene catalysts being one of them.
- a Ziegler-Natta catalysed polymer is obtained via the interaction of an organometallic compound or hydride of a Group I-III metal with a derivative of a Group IV-VIII transition metal.
- An example of a (modified) Ziegler-Natta catalyst is a catalyst based on titanium tetra chloride and the organometallic compound triethylaluminium.
- a difference between metallocene catalysts and Ziegler Natta catalysts is the distribution of active sites.
- Ziegler Natta catalysts are heterogeneous and have many active sites. Consequently polymers produced with these different catalysts will be different regarding for example the molecular weight distribution and the comonomer distribution.
- the various processes may be divided into solution polymerisation processes employing homogeneous (soluble) catalysts and processes employing supported (heterogeneous) catalysts.
- the latter processes include both slurry and gas phase processes.
- linear low density polyethylene the term “linear” means that the polymer lacks measurable or demonstrable long chain branches, that is, the polymer is substituted with an average of less than 0.01 long chain branch/1000 carbon atoms.
- Long chain branching means a chain length longer than the short chain branch that results from the incorporation of the ⁇ -olefin(s) into the polymer backbone.
- Each long chain branch will have the same comonomer distribution as the polymer backbones and can be as long as the polymer backbone to which it is attached.
- the amount of incorporation of the at least one other olefin, for example an ⁇ -olefin in the polyethylene is expressed by the amount of branches per 1000 carbon atoms.
- the number average molecular weight (Mn) of the polyolefin, for example polyethylene, for example LLDPE of the invention may vary between wide ranges and may for example be in the range from 1000 to 200000Da.
- the Mn of the polyolefin of the invention may be at least 1500, for example at least 2000, for example at least 20,000, for example at least 50,000 and/or for example at most 150,000, for example at most 110,000, for example at most 100,000, for example at most 70,000.
- the weight average molecular weight (Mw) of the polyolefin, for example polyethylene, for example LLDPE of the invention may also vary between wide ranges and may for example be in the range from 1500 to 500000.
- the Mw of the polyolefin of the invention may be at least 2500, for example at least 10,000, for example at least 50,000, for example at least 100,000 and/or for example at most 400,000, for example at least 350,000, for example at most 300,000, for example at most 250,000.
- the Mw and Mn are determined using SEC (Size Exclusion Chromatography) using 1,2,4-trichlorobenzene as an eluent, and calibrated using linear polyethylene standards.
- the molecular weight distribution (that is Mw/Mn) of the polyolefin of the invention may for example vary from from 2 to 5, from 2.1 to 4 or from 2.5 to 3.5.
- the crystallinity temperature (Tc) of the polyolefin of the invention may for example be in the range from 90 to 120°C.
- the melt temperature (Tm) of the polyolefin of the invention may for example be in the range from 100 to 140°C.
- the T m and T c are determined using Differential Scanning Calorimetry according to ASTM D 3418-08 using a scan rate of 10°C/min on a sample of 10mg and using the second heating cycle
- the polyolefin may be mixed with suitable additives.
- suitable additives for polyethylene include but are not limited to the additives usually used for polyethylene, for example antioxidants, nucleating agents, acid scavengers, processing aids, lubricants, surfactants, blowing agents, ultraviolet light absorbers, quenchers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, pigments, dyes and fillers, and cure agents such as peroxides.
- the additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight % based on the total composition.
- the polyolefins and compositions comprising said polyolefins may suitably be used for the manufacture of articles.
- the polyolefins and compositions may be manufactured into film, for example by compounding, extrusion, film blowing or casting or other methods of film formation to achieve, for example uniaxial or biaxial orientation.
- films include blown or cast films formed by coextrusion (to form multilayer films) or by lamination and may be useful as films for packaging, for example as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications, agricultural films and sheets.
- LC-MS liquid chromatograph-mass spectrometer
- An Xterra C18 (50 mm X 4.6 mm; 5 microns) column was used for separating the components by liquid chromatography.
- a H and 13 C NMR spectra for all the compounds were recorded on a 300 MHz Bruker NMR spectrometer.
- CDCl3 was used as the solvent for NMR.
- Step 1 Synthesis of 1-bromo-2-(N- tert -butyl)benzene- tert -butyl 2-bromoaniline
- Step 2 Synthesis of 1-(N- tert butyl)-2-(2-indenyl) benzene:
- the sample was dissolved completely in diethyl ether.
- the solution was cooled to -78°C.
- n-BuLi (2.49ml; 1.6N in hexanes; 0.00399 moles) was added to this solution drop wise.
- the color gradually changed to yellow and the solution became hazy.
- the cold bath was removed after ⁇ 30min and solution left to stir at RT for 4hrs.
- the solution became clear and the color of the solution gradually became brown with a greenish tinch.
- the solution was again cooled to -78°C and solid ZrCl4 (0.442g; 0.0019 moles) was added.
- the temperature of the solution was slowly brought to RT and left the solution for stirring for 2h.
- the color of the solution was turned to brown and solid was precipitated. Stopped the stirring and ether was taken to the other arm of the Schlenk by filtration. Solid was washed with ether and dried.
- the color of the solution became yellow and gradually changed to brown and greenish brown in about 2h.
- the solution was again cooled to -78oC and solid ZrCl4 (0.35 g; 0.0015 moles) was added. Immediately after the addition of ZrCI4, the color of the solution was changed to yellow.
- the temperature of the solution was slowly brought to RT and left the solution for stirring for 2h.
- the color of the solution was turned to brown and solid was precipitated. Stopped the stirring and ether was taken to the other arm of the Schlenk by filtration. Solid was washed with ether and dried.
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Claims (4)
- Prozess zur Herstellung der Metallocenkomplexe gemäß Formel 5a) Reagieren von 2-Bromphenyl-Boronsäure mit 1,8-Diaminonaphthalen, um eine geschützte Verbindung (Formel 13) zu bildenb) Reagieren der geschützten Verbindung (13) mit einer Verbindung der Formel 14c) Entschützen der geschützten Verbindung durch eine Reaktion mit einer Säure, um die Verbindung gemäß Formel 16 zu erreichend) Reagieren der Verbindung (16) mit N-substituiertem 2-Bromanilin (Formel 7)e) Erzeugen von Anionen der Ligandenvorläufer (11) mit einer organischen oder anorganischen Basef) Reagieren des Anions des Ligandenvorläufers mit (Me2N)aMQk, wobei Me Methyl ist; M ein Metall ist, ausgewählt aus Lanthaniden oder Übergangsmetallen aus Gruppe 3, 4, 5 oder 6 des Periodensystems der Elemente, bevorzugt M Zr ist; Q ein anionischer Ligand für M ist, bevorzugt Q Cl oder Methyl ist; k die Anzahl von Q-Gruppen ist und der Valenz von M minus 2 gleicht; und a der Valenz von M minus k gleicht, um einen Metallocenkomplex gemäß Formel 5 zu ergeben.
- Prozess nach Anspruch 1, wobei R t-Butyl ist.
- Prozess nach einem der Ansprüche 1-2, wobei M Zr ist.
- Prozess nach einem der Ansprüche 1-3, wobei Q Cl oder Methyl ist.
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EP14747576.8A EP3027631B1 (de) | 2013-08-01 | 2014-07-29 | Prozess zur herstellung von verbrückten metallocenkomplexen geeignet für die olefinpolymerisierung |
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US5272236A (en) | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
NL9201970A (nl) | 1992-11-11 | 1994-06-01 | Dsm Nv | Indenylverbindingen en katalysatorcomponenten voor de polymerisatie van olefinen. |
FI945958A (fi) * | 1993-12-21 | 1995-06-22 | Hoechst Ag | Menetelmä polyolefiinien valmistamiseksi |
US6342622B1 (en) | 1999-06-11 | 2002-01-29 | Dsm B.V. | Indenyl compounds for the polymerization of olefins |
DE10003581A1 (de) * | 2000-01-28 | 2001-08-02 | Bayer Ag | Metallorganische Verbindungen mit anellierten Indenyl Liganden |
US7807762B2 (en) * | 2005-12-30 | 2010-10-05 | Lg Chem, Ltd. | Catalyst composition comprising Group 4 transition metal complexes and method for preparing polyolefins using the same |
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Title |
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DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; LENSINK, CORNELIS ET AL: "Dichloro{N-[2-(.eta.5-indenyl)ethyl]-p-tolylsulfonamido-.kappa.N}titanium", retrieved from STN Database accession no. 2002:411896 * |
JYE-SHANE YANG ET AL: "Excited-State Behavior of N -Phenyl-Substituted trans- 3-Aminostilbenes: Where the " m -Amino Effect" Meets the "Amino-Conjugation Effect"", JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY,KINETICS, ENVIRONMENT AND GENERAL THEORY, vol. 109, no. 29, 1 July 2005 (2005-07-01), US, pages 6450 - 6456, XP055676336, ISSN: 1089-5639, DOI: 10.1021/jp0517807 * |
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